Thermoplastic olefin elastomer composition for powder molding, powder for powder molding, and molded object

ABSTRACT

An olefin-based thermoplastic elastomer composition for powder molding is described. The olefin-based thermoplastic elastomer composition produces no emission of poisonous gas at incineration. It is hardly whitened on bending and has excellent flexibility.

This application is the national phase under 35 U.S.C. §371 of PCTInternational Application No. PCT/JP98/05702 which has an Internationalfiling date of Dec. 17, 1998, which designated the United States ofAmerica.

TECHNICAL FIELD

The present invention relates to an olefin-based thermoplastic elastomercomposition for powder molding, powder for powder molding, and a moldedarticle. More particularly, the present invention relates to anolefin-based thermoplastic elastomer composition for powder molding,which makes the best use of the merit of an olefin-based material suchas no generation of poisonous gas at incineration, and is hardlywhitened on bending and excellent in flexibility; powder for powdermolding prepared from said composition; and a molded article obtained bypowder molding said powder.

BACKGROUND ARTS

Hitherto, molded articles having complicated patterns such as leathergrains, stitches and the like on its surface have been used as themolded articles of interior parts of automobiles, and the like. As suchskin material, vinyl chloride-based resin molded articles are widelyknown. However, the vinyl chloride-based resin molded articles had aproblem of requiring a special incineration facility because hydrogenchloride gas and the like are generated at incineration disposal afteruse.

The molded article of a composition composed of a polyolefin-based resinand an ethylene-α-olefin-based copolymer is proposed as that solving theproblem (Japanese Patent Publication (Kokai) Hei Nos. 5-1183 and5-5050). However, since the molded article has a property of beingeasily whitened on bending in comparison with the vinyl chloride-basedresin molded article, and therefore, when said molded article is removedfrom a mold after production or when said molded article ispreliminarily formed in a desired shape or the like after production,the portion bent is whitened and appearance inferiority tends to occur.Additionally, there has been a problem of being inferior in the touchbecause of being poor in flexibility.

Under these circumstances, the subject to be solved by the presentinvention is to provide an olefin-based thermoplastic elastomercomposition for powder molding. which makes the best use of the merit ofan olefin-based material such as no generation of poisonous gas atincineration and is hardly whitened on bending and excellent inflexibility; powder for powder molding prepared from said composition;and a molded article obtained by powder molding said powder.

DISCLOSURE OF THE INVENTION

Namely, the first invention among the present invention relates to anolefin-based thermoplastic elastomer composition for powder moldingwhich contains 5 to 93% by weight of (a) and 7 to 95% by weight of (b){(a)+(b)=100% by weight} described below, and is prepared from anolefin-based thermoplastic elastomer composition having a complexdynamic viscosity η*(1) at 250° C. of 1.5×10⁵ poise or less as measuredat an vibration frequency of 1 radian/sec. and a Newtonian viscosityindex n of 0.67 or less as calculated by the equation [I] describedbelow:

(a): a polyolefin-based resin; and

(b): at least one of (b1) and (b2) described below:

(b1): a propylene-1-butene-based copolymer rubber having a Shore Ahardness of 70 or less as measured in accordance with ASTM D2240 and anintrinsic viscosity [η] of 0.3 dl/g or more as measured at a temperatureof 70° C. in xylene, and

(b2): a propylene-α-olefin-ethylene-based copolymer rubber having aShore A hardness of 70 or less as measured in accordance with ASTM D2240and an intrinsic viscosity [η] of 0.3 dl/g or more as measured at atemperature of 70° C. in xylene and comprising propylene, an α-olefinhaving 4 to 20 carbon atoms and ethylene.

n={log η*(1)−log η*(100)}/2  Equation [I]

(in the above-mentioned equation, η*(1) represents a complex dynamicviscosity at 250° C. measured at a vibration frequency of 1 radian/sec.,and η*(100) represents a complex dynamic viscosity at 250° C. measuredat a vibration frequency of 100 radian/sec.)

Further, the second invention among the present invention relates topowder for powder molding prepared from the olefin-based thermoplasticelastomer composition of the above-mentioned first invention.

Further, the third invention among the present invention relates to amolded article obtained by powder molding the powder for powder moldingof the above-mentioned second invention.

BEST MODE FOR PRACTICING THE INVENTION

The polyolefin-based resin (a) used in the present invention includes acrystalline polymer or copolymer obtained by polymerizing orcopolymerizing one or more of olefins (for example, a propylenehomopolymer, a copolymer of propylene with ethylene and/or an α-olefinother than propylene, an ethylene homopolymer, a copolymer of ethylenewith an α-olefin other than ethylene, and the like), a copolymerobtained by copolymerizing one or more of olefins at 2 steps or more(for example, a propylene-ethylene block copolymer which is obtained bycarrying out the homopolymerization of propylene in the first step andcarrying out the copolymerization of propylene with ethylene in thesecond step, a propylene-olefin copolymer which is obtained by carryingout the copolymerization of propylene with an olefin in the first step,in the second step and in successive steps, respectively and hasdifferent copolymerization compositions at respective steps, and thelike). Preferable (a) is a propylene-based polymer, namely, a propylenehomopolymer or a propylene-based copolymer mainly containing propylene.

(b) of the present invention is (b1): a propylene-1-butene-basedcopolymer rubber having a Shore A hardness of 70 or less as measured inaccordance with ASTM D2240 and an intrinsic viscosity [η] of 0.3 dl/g ormore as measured at a temperature of 70° C. in xylene, and/or (b2): apropylene-α-olefin-ethylene-based copolymer rubber having a Shore Ahardness of 70 or less as measured in accordance with ASTM D2240 and anintrinsic viscosity [η] of 0.3 dl/g or more as measured at a temperatureof 70 in xylene and comprising propylene, an α-olefin having 4 to 20carbon atoms and ethylene.

The Shore A hardness measured in accordance with ASTM D2240 is 70 orless and preferably 60 or less in (b1) and (b2). When the hardness istoo high, the thermoplastic elastomer obtained is inferior inflexibility.

The intrinsic viscosity [η] measured at 70° C. in xylene is 0.3 dl/g ormore and preferably 0.5 dl/g or more in (b1) and (b2). When theintrinsic viscosity is too low, the tensile elongation property of thethermoplastic elastomer obtained is poor.

The measurement of the intrinsic viscosity [η] is carried out at 70° C.in xylene using a Ubbelohde viscometer. A sample of 300 mg is dissolvedin 100 ml of xylene to prepare a solution having a concentration of 3mg/ml. Said solution is further diluted to concentrations of 1/2, 1/3and 1/5, and each of the solutions is measured in a constant-temperaturewater bath of 70° C. (±0.1° C.). The measurement is repeated three timesat the respective concentrations, and an average of the values obtainedis used. Herein, the intrinsic viscosity [η] is the extrapolated valueof the reduced viscosity at a concentration of zero when values obtainedby setting reduced viscosity (a value determined by ((η/η₀)−1)/C whenthe viscosity of a solution is η, the viscosity of a solvent is η₀, andthe concentration of the solution is C) to an axis of ordinate, andsetting the concentration to an axis of abscissa, are plotted, and anapproximate straight line is drawn from these points.

In (b1) and (b2), those having neither crystal-melting peak norcrystallization peak at measurement by a differential scanningcalorimeter (DSC) are preferable. When the conditions are not satisfied,the thermoplastic elastomer obtained happens to be inferior inflexibility. As the differential scanning calorimeter, for example,DSC220C manufactured by Seiko Electronics Industry, Co, Ltd. is used andboth of the measurements at temperature-elevating process andtemperature-lowering process are carried out at a rate of 10° C./min.

In (b1) and (b2), those having a molecular weight distribution (Mw/Mn)of 3 or less as measured by gel permeation chromatography (GPC) arepreferable. When the molecular weight distribution is too broad, thestickiness of the thermoplastic elastomer is occasionally enlarged. Themeasurement of molecular weight distribution by GPC is carried out underthe conditions below, for example, using 150C/GPC apparatus manufacturedby Waters Co, Ltd. Elution temperature is 140° C., a column used is, forexample, Shodex Packed Column A-80M manufactured by Showa Denko K.K.,and a polystyrene (for example, molecular weight=68-8,400,000manufactured by Toso Co., Ltd.) is used as a molecular weight standardsubstance. A polystyrene-reduced weight average molecular weight (Mw)and number average molecular weight (Mn) are obtained, and further, theratio (Mw/Mn) is referred to as molecular weight distribution. A samplefor measurement is prepared by dissolving about 5 mg of a polymer in 5ml of o-dichlorobenzene to be a concentration of about 1 mg/ml. 400 μLof the sample solution obtained is injected, the flow rate of elutionsolvent is 1.0 ml/min., and it is detected by a refractive indexdetector.

The 1-butene content in (b1) is preferably 0.5 to 90% by mole andfurther preferably 1 to 70% by mole. When said content is too small, theflexibility of the olefin-based thermoplastic elastomer composition isoccasionally poor, and on the other hand, when said content is toolarge, the molecular weight of a copolymer is remarkably lowered and thescratch resistance of the olefin-based thermoplastic elastomercomposition is occasionally poor.

The propylene content and α-olefin content in (b2) preferably have therelations below;

y/(100−x)≧0.3,

more preferably y/(100−x)≧0.4, and

further preferably y/(100−x)≧0.5.

When the contents deviate from the range, the flexibility of theolefin-based thermoplastic elastomer composition is occasionally poor.Moreover, in the above expressions, x represents a propylene molarcontent (% by mole) in the copolymer and y represents a molar content (%by mole) of the α-olefin having 4 to 20 carbons in the copolymer.

The propylene content in (b2) is preferably 90% by mole or less whenlow-temperature resistance is required in particular, more preferably80% by mole or less, further preferably 70% by mole or less, preferably60% by mole or less in particular, and most preferably 50% by mole orless. When the content deviates from the range, the low-temperatureimpact of the olefin-based thermoplastic elastomer composition isoccasionally poor.

In (b1) and (b2), a non-conjugated diene such as 1,4-hexadiene,1,6-octadiene, dicyclopentadiene, 2-methyl-2,5-norbonadiene,5-ethylidene-2-norbornene or the like and an aromatic vinyl compoundsuch as styrene, α-methylstyrene, 2,4-dimethylstyrene, p-methylstyrene,or the like may be copolymerized.

In (b1) and (b2), a portion insoluble in boiling n-heptane is preferably5% by weight or less and further preferably 3% by weight or less. Whenthe insoluble portion is too much, the thermoplastic elastomercomposition obtained is occasionally inferior in flexibility.

Further, in (b1) and (b2), a portion soluble in boiling methyl acetateis preferably 2% by weight or less. When said soluble portion is toomuch, the stickiness of the thermoplastic elastomer composition isoccasionally enlarged.

The configuration of a propylene and/or 1-butene side chain in (b1) andthe configuration of a propylene and/or α-olefin side chain in (b2) arepreferably an atactic structure. The configuration being an atacticstructure indicates a case that the configuration of the side chain ofpropylene sequence in a copolymer is an atactic structure, a case thatthe configuration of the side chain of 1-butene or α-olefin sequence ina copolymer is an atactic structure, and a case that the configurationof the side chain of propylene/1-butene mixed sequence in a copolymer orpropylene/α-olefin mixed sequence in a copolymer is an atacticstructure. The atactic structure can be confirmed, for example, by thefact that when propylene is homopolymerized using the transition metalcomplex of the catalyst component used in the polymerization of (b1) and(b2), the homopolypropylene obtained has a structure in which F(1) valuedefined by the equation described below using the intensities ofrespective signals, [mm], [mr] and [rr] attributed to mm, mr and rr ofthe methyl carbon of propylene which can be determined by ¹³C-NMRspectrum, is 40 or more and 60 or less, preferably 43 or more and 57 orless, and further preferably 45 or more and 55 or less.

F(1)=100×[mr]/([mm]+[mr]+[rr])

Similarly, concerning (b1) and (b2), the atactic structure can be alsoconfirmed by the fact that a value corresponding to F(1) determined byusing the respective signal intensities attributed to mm, mr and rr ofthe methyl carbon of propylene, the branched methylene carbon of1-butene, the branched terminal methyl carbon of 1-butene, and the like,is within the above-mentioned range. When (b1) and (b2) have not theatactic structure, the thermoplastic elastomer composition obtained isoccasionally inferior in flexibility because of its high hardness.Further, the attributions of the methyl carbon of propylene, thebranched methylene carbon of 1-butene or α-olefin, the branched terminalmethyl carbon of 1-butene or α-olefin, and the like can be carried outby referring to, for example, T. Asakura, “Macromolecules, Vol.24(1991),page 2334” and “High Polymer Analysis Handbook (1995), New Edition”published by Kinokuniya Shoten Co., Ltd.

(b1) and (b2) can be suitably produced by copolymerizing propylene and1-butene or propylene, an α-olefin and ethylene with a polymerizationcatalyst which provides a polypropylene having neither crystal-meltingpeak nor crystallization peak at measurement by a differential scanningcalorimeter (DSC), which is obtained by polymerizing propylene in thepresence of the polymerization catalyst.

As the most suitable polymerization catalyst for producing (c1) and(c2), a polymerization catalyst prepared by using (A) described below,and (B) described below and/or (C) described below:

(A): a transition metal complex represented by the following generalformula [I]:

(wherein M¹ represents a transition metal atom of Group IV of thePeriodic Table of the Elements; A represents an atom of Group XVI of thePeriodic Table of the Elements; J represents an atom of Group XIV of thePeriodic Table of the Elements; Cp¹ represents a group having acyclopentadiene type anion skeleton; X¹, X², R¹, R², R³, R⁴, R⁵ and R⁶independently represent a hydrogen atom, a halogen atom, an alkyl group,an aralkyl group, an aryl group, a substituted silyl group, an alkoxygroup, an aralkyloxy group, an aryloxy group or a di-substituted aminogroup; and R¹, R², R³, R⁴, R⁵ and R⁶ may be optionally combined witheach other to form a ring);

(B): at least one aluminum compound selected from the following (B1) to(B3)

(B1) an organoaluminum compound represented by the general formula E¹_(d)AlZ_(3−d),

(B2) a cyclic aluminoxane having a structure represented by the generalformula {—Al(E²)—O—}_(e), and

(B3) a linear aluminoxane having a structure represented by the generalformula E³{—Al(E³)—O—}_(f)AlE³ ₂ (wherein E¹, E² and E³ respectivelyrepresents a hydrocarbon group, all of E¹, E² and E³ may be the same ordifferent; Z represents a hydrogen atom or a halogen atom, and all of Zmay be the same or different; d represents a numeral satisfying 0<d≦3; erepresents an integer of not less than 2; and f represents an integer ofnot less than 1); and

(C): a boron compound of any one of the following (C1) to (C3);

(C1) a boron compound represented by the general formula BQ¹Q²Q³,

(C2) a boron compound represented by the general formula G⁺(BQ¹Q²Q³Q⁴)⁻,and

(C3) a boron compound represented by the general formula(L—H)⁺(BQ¹Q²Q³Q⁴)⁻

(wherein B represents a boron atom in the trivalent valence state; Q¹ toQ⁴ may be the same or different and represent a halogen atom, ahydrocarbon group, a halogenated hydrocarbon group, a substituted silylgroup, an alkoxy group or a di-substituted amino group; G+ represents aninorganic or organic cation; L represents a neutral Lewis base; and(L—H)+ represents a Brφnsted acid).

(A) Transition Metal Complex

In the general formula [I], the transition metal atom represented by M¹means a transition metal element of Group IV of the Periodic Table ofthe Elements (IUPAC Inorganic Chemistry Nomenclature, Revised Edition,1989), and examples thereof include titanium atom, zirconium atom,hafnium atom, etc. Among them, titanium atom or zirconium atom ispreferred.

Examples of the atom of Group XVI of the Periodic Table of the Elementsas for A in the general formula [I] include oxygen atom, sulfur atom,selenium atom, etc, preferably oxygen atom.

Examples of the atom of Group XIV of the Periodic Table of the Elementsas for J in the general formula [I] include a carbon atom, silicon atom,germanium atom, etc., preferably a carbon atom or silicon atom.

The group having a cyclopentadiene anion skeleton, as for thesubstituent Cp¹, includes, for example, aη⁵-(substituted)cyclopentadienyl group, η⁵-(substituted)indenyl group,η⁵-(substituted)fluorenyl group, etc. Specific examples thereof includea η⁵-cyclopentadienyl group, η⁵-methylcyclopentadienyl group,η⁵-dimethylcyclopentadienyl group, η⁵-trimethylcyclopentadienyl group,η⁵-tetramethylcyclopentadienyl group, η⁵-ethylcyclopentadienyl group,η⁵-n-propylcyclopentadienyl group, η⁵-isopropylcyclopentadienyl group,η⁵-n-butylcyclopentadienyl group, η⁵-sec-butylcyclopentadienyl group,η⁵-tert-butylcyclopentadienyl group, η⁵-n-pentylcyclopentadienyl group,η⁵-neopentylcyclopentadienyl group, η⁵-n-hexylcyclopentadienyl group,η⁵-n-octylcyclopentadienyl group, η⁵-phenylcyclopentadienyl group,η⁵-naphthylcyclopentadienyl group, η⁵-trimethylsilylcyclopentadienylgroup, η⁵-triethylsilylcyclopentadienyl group,η⁵-tert-butyldimethylsilylcyclopentadienyl group, η⁵-indenyl group,η⁵-methylindenyl group, η⁵-dimethylindenyl group, η⁵-ethylindenyl group,η⁵-n-propylindenyl group, η⁵-isopropylindenyl group, η⁵-n-butylindenylgroup, η⁵-sec-butylindenyl group, η⁵-tert-butylindenyl group,η⁵-n-pentylindenyl group, η⁵-neopentylindenyl group, η⁵-n-hexylindenylgroup, η⁵-n-octylindenyl group, η⁵-n-decylindenyl group,η⁵-phenylindenyl group, η⁵-methylphenylindenyl group, η⁵-naphthylindenylgroup, η⁵-trimethylsilylindenyl group, η⁵-trimethylsilylindenyl group,η⁵-tert-butyldimethylsilylindenyl group, η⁵-tetrahydroindenyl group,η⁵-fluorenyl group, η⁵-methylfluorenyl group, η⁵-dimethylfluorenylgroup, η⁵-ethylfluorenyl group, η⁵-diethylfluorenyl group,η⁵-n-propylfluorenyl group, η⁵-di-n-propylfluorenyl group,η⁵-isopropylfluorenyl group, η⁵-diisopropylfluorenyl group,η⁵-n-butylfluorenyl group, η⁵-sec-butylfluorenyl group,η⁵-tert-butylfluorenyl group, η⁵-di-n-butylfluorenyl group,η⁵-di-sec-butylfluorenyl group, η⁵-di-tert-butylfluorenyl group,η⁵-n-pentylfluorenyl group, η⁵-neopentylfluorenyl group,η⁵-n-hexylfluorenyl group, η⁵-n-octylfluorenyl group,η⁵-n-decylfluorenyl group, η⁵-n-dodecylfluorenyl group,η⁵-phenylfluorenyl group, η⁵-diphenylfluorenyl group,η⁵-methylphenylfluorenyl group, η⁵-naphthylfluorenyl group,η⁵-trimethylsilylfluorenyl group, η⁵-bis-trimethylsilylfluorenyl group,η⁵-triethylsilylfluorenyl group, η⁵-tert-butyldimethylsilylfluorenylgroup, etc. Among them, η⁵-cyclopentadienyl group,η⁵-methylcyclopentadienyl group, η⁵-tert-butylcyclopentadienyl group,η⁵-tetramethylcyclopentadienyl group, η⁵-indenyl group or η⁵-fluorenylgroup is particularly preferred.

Examples of the halogen atom in the substituent X¹, X², R¹, R², R³, R⁴,R⁵ or R⁶ include fluorine atom, chlorine atom, bromine atom and iodineatom, preferably chlorine atom or bromine atom, more preferably chlorineatom.

As the alkyl group in the substituent X¹, X², R¹, R², R³, R⁴, R⁵ or R⁶,an alkyl group having 1 to 20 carbon atoms is preferred. Examplesthereof include a methyl group, ethyl group, n-propyl group, isopropylgroup, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group,neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decylgroup, n-dodecyl group, n-pentadecyl group, n-eicosyl group, etc., morepreferably a methyl group, ethyl group, isopropyl group, tert-butylgroup or amyl group.

All of these alkyl groups may be substituted with a halogen atom(fluorine atom, chlorine atom, bromine atom or iodine atom). Examples ofthe alkyl group having 1 to 20 carbon atoms, which is substituted withthe halogen atom, include fluoromethyl group, difluoromethyl group,trifluoromethyl group, chloromethyl group, dichloromethyl group,trichloromethyl group, bromomethyl group, dibromomethyl group,tribromomethyl group, iodomethyl group, diiodomethyl group,triiodomethyl group, fluoroethyl group, difluoroethyl group,trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group,chloroethyl group, dichloroethyl group, trichloroethyl group,tetrachloroethyl group, pentachloroethyl group, bromoethyl group,dibromoethyl group, tribromoethyl group, tetrabromoethyl group,pentabromoethyl group, perfluoropropyl group, perfluorobutyl group,perfluoropentyl group, perfluorohexyl group, perfluorooctyl group,perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosylgroup, perchloropropyl group, perchlorobutyl group, perchloropentylgroup, perchlorohexyl group, perchlorooctyl group, perchlorododecylgroup, perchloropentadecyl group, perchloroeicosyl group, perbromopropylgroup, perbromobutyl group, perbromopentyl group, perbromohexyl group,perbromooctyl group, perbromododecyl group, perbromopentadecyl group,perbromoeicosyl group, etc.

All of these alkyl groups may be partially substituted with an alkoxygroup such as methoxy group, ethoxy group, etc., an aryloxy group suchas phenoxy group, etc. or an aralkyloxy group such as benzyloxy group,etc.

As the aralkyl group in the substituent X¹, X², R¹, R², R³, R⁴, R⁵ orR⁶, an aralkyl group having 7 to 20 carbon atoms is preferred. Examplesthereof include a benzyl group, (2-methylphenyl)methyl group,(3-methylphenyl)methyl group, (4-methylphenyl)methyl group,(2,3-dimethylphenyl)methyl group, (2,4-dimethylphenyl)methyl group,(2,5-dimethylphenyl)methyl group, (2,6-dimethylphenyl)methyl group,(3,4-dimethylphenyl)methyl group, (4,6-dimethylphenyl)methyl group,(2,3,4-timethylphenyl)methyl group, (2,3,5-timethylphenyl)methyl group,(2,3,6-timethylphenyl)methyl group, (3,4,5-timethylphenyl)methyl group,(2,4,6-timethylphenyl)methyl group, (2,3,4,5-tetramethylphenyl)methylgroup, (2,3,4,6-tetramethylphenyl)methyl group,(2,3,5,6-tetramethylphenyl)methyl group, (pentamethylphenyl)methylgroup, (ethylphenyl)methyl group, (n-propylphenyl)methyl group,(isopropylphenyl)methyl group, (n-butylphenyl)methyl group,(sec-butylphenyl)methyl group, (tert-butylphenyl)methyl group,(n-pentylphenyl)methyl group, (neopentylphenyl)methyl group,(n-hexylphenyl)methyl group, (n-octylphenyl)methyl group,(n-decylphenyl)methyl group, (n-dodecylphenyl)methyl group,(n-tetradecylphenyl)methyl group, naphthylmethyl group,anthracenylmethyl group, etc., more preferably a benzyl group.

All of these aralkyl groups may be partially substituted with a halogenatom (fluorine atom, chlorine atom, bromine atom or iodine atom), analkoxy group such as a methoxy group, ethoxy group, etc., an aryloxygroup such as a phenoxy group, etc. or an aralkyloxy group such as abenzyloxy group, etc.

As the aryl group in the substituent X¹, X², R¹, R², R³, R⁴, R⁵ or R⁶,an aryl group having 6 to 20 carbon atoms is preferred. Examples thereofinclude a phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group,2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group,3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group,2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group,2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group,2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group,2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenylgroup, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group,sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group,neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group,n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group,naphthyl group, anthracenyl group, etc., more preferably a phenyl group.

All of these aryl groups may be partially substituted with a halogenatom (fluorine atom, chlorine atom, bromine atom or iodine atom), analkoxy group such as a methoxy group, ethoxy group, etc., an aryloxygroup such as a phenoxy group, etc. or an aralkyloxy group such as abenzyloxy group, etc.

The substituted silyl group in the substituent X¹, X², R¹, R², R³, R⁴,R⁵ or R⁶ is a silyl group substituted with a hydrocarbon group, andexamples of the hydrocarbon group include an alkyl group having 1 to 10carbon atoms, such as a methyl group, ethyl group, n-propyl group,isopropyl group, n-butyl group, sec-butyl group, tert-butyl group,isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, etc.,and an aryl group such as a phenyl group. Examples of the substitutedsilyl group having 1 to 20 carbon atoms include mono-substituted silylgroup having 1 to 20 carbon atoms, such as methylsilyl group, ethylsilylgroup, phenylsilyl group, etc.; di-substituted silyl group having 2 to20 carbon atoms, such as a dimethylsilyl group, diethylsilyl group,diphenylsilyl group, etc.; and tri-substituted silyl group having 3 to20 carbon atoms, such as a trimethylsilyl group, triethylsilyl group,tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilylgroup, tri-sec-butylsilyl group, tri-tert-butylsilyl group,tri-isobutylsilyl group, tert-butyl-dimethylsilyl group,tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilylgroup, triphenylsilyl group, etc., preferably a trimethylsilyl group,tert-butyldimethylsilyl group or triphenylsilyl group.

All of the hydrocarbon groups of these substituted silyl groups may bepartially substituted with a halogen atom (fluorine atom, chlorine atom,bromine atom or iodine atom), an alkoxy group such as a methoxy group,ethoxy group, etc., an aryloxy group such as phenoxy group, etc. or anaralkyloxy group such as benzyloxy group, etc.

As the alkoxy group in the substituent X¹, X², R¹, R², R³, R⁴, R⁵ or R⁶,an alkoxy group having 1 to 20 carbon atoms is preferred. Examplesthereof include a methoxy group, ethoxy group, n-propoxy group,isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group,n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group,n-dodecoxy group, n-pentadecoxy group, n-eicosoxy group, etc., morepreferably a methoxy group, ethoxy group or tert-butoxy group.

All of these alkoxy groups may be partially substituted with a halogenatom (fluorine atom, chlorine atom, bromine atom or iodine atom), analkoxy group such as a methoxy group, ethoxy group, etc., an aryloxygroup such as a phenoxy group, etc. or an aralkyloxy group such as abenzyloxy group, etc.

As the aralkyloxy group in the substituent X¹, X², R¹, R², R³, R⁴, R⁵ orR⁶, an aralkyloxy group having 7 to 20 carbon atoms is preferred.Examples thereof include a benzyloxy group, (2-methylphenyl)methoxygroup, (3-methylphenyl)methoxy group, (4-methylphenyl)methoxy group,(2,3-dimethylphenyl)methoxy group, (2,4-dimethylphenyl)methoxy group,(2,5-dimethylphenyl)methoxy group, (2,6-dimethylphenyl)methoxy group,(3,4-dimethylphenyl)methoxy group, (3,5-dimethylphenyl)methoxy group,(2,3,4-trimethylphenyl)methoxy group, (2,3,5-trimethylphenyl)methoxygroup, (2,3,6-trimethylphenyl)methoxy group,(2,4,5-trimethylphenyl)methoxy group, (2,4,6-trimethylphenyl)methoxygroup, (3,4,5-trimethylphenyl)methoxy group,(2,3,4,5-tetramethylphenyl)methoxy group,(2,3,4,6-tetramethylphenyl)methoxy group,(2,3,5,6-tetramethylphenyl)methoxy group, (pentamethylphenyl)methoxygroup, (ethylphenyl)methoxy group, (n-propylphenyl)methoxy group,(isopropylphenyl)methoxy group, (n-butylphenyl)methoxy group,(sec-butylphenyl)methoxy group, (tert-butylphenyl)methoxy group,(n-hexylphenyl)methoxy group, (n-octylphenyl)methoxy group,(n-decylphenyl)methoxy group, (n-tetradecylphenyl)methoxy group,naphthylmethoxy group, anthracenylmethoxy group, etc., more preferably abenzyloxy group.

All of these aralkyloxy groups may be partially substituted with ahalogen atom (fluorine atom, chlorine atom, bromine atom or iodineatom), an alkoxy group such as a methoxy group, ethoxy group, etc., anaryloxy group such as a phenoxy group, etc. or an aralkyloxy group suchas a benzyloxy group, etc.

As the aryloxy group in the substituent X¹, X², R¹, R², R³, R⁴, R⁵ orR⁶, an aralkyloxy group having 6 to 20 carbon atoms is preferred.Examples thereof include a phenoxy group, 2-methylphenoxy group,3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group,2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group,2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group,3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group,2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group,2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group,3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group,2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group,pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group,isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group,tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group,n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group,anthracenoxy group, etc.

All of these aryloxy groups may be partially substituted with a halogenatom (fluorine atom, chlorine atom, bromine atom or iodine atom), analkoxy group such as a methoxy group, ethoxy group, etc., an aryloxygroup such as a phenoxy group, etc. or an aralkyloxy group such as abenzyloxy group, etc.

The di-substituted amino group in the substituent X¹, X², R¹, R², R³,R⁴, R⁵ or R⁶ is an amino group substituted with two hydrocarbon groups,and examples of the hydrocarbon group include alkyl group having 1 to 10carbon atoms, such as a methyl group, ethyl group, n-propyl group,isopropyl group, n-butyl group, sec-butyl group, tert-butyl group,isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, etc.;aryl group having 6 to 10 carbon atoms, such as phenyl group, etc.; andaralkyl group having 7 to 10 carbon atoms. Examples of thedi-substituted amino group substituted with the hydrocarbon group having1 to 10 carbon atoms include dimethylamino group, diethylamino group,di-n-propylamino group, diisopropylamino group, di-n-butylamino group,di-sec-butylamino group, di-tert-butylamino group, di-isobutylaminogroup, tert-butylisopropylamino group, di-n-hexylamino group,di-n-octylamino group, di-n-decylamino group, diphenylamino group,bistrimethylsilylamino group, bis-tert-butyldimethylsilylamino group,etc., preferably a dimethylamino group or diethylamino group.

The substituent R¹, R², R³, R⁴, R⁵ and R⁶ may be optionally combinedwith each other to form a ring.

R¹ is preferably an alkyl group, an aralkyl group, an aryl group or asubstituted silyl group.

Preferably, each of X¹ and X² is independently a halogen atom, an alkylgroup, an aralkyl group, an alkoxy group, an aryloxy group or adi-substituted amino group, more preferably halogen atom.

Examples of the transition metal complex (A) represented by the formula[I] include transition metal complexes wherein J is a carbon atom in thegeneral formula [I], such asmethylene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,methylene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride,methylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, methylene(cyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,methylene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(cyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,methylene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride, methylene(fluorenyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride, methylene(fluorenyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,methylene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, methylene(fluorenyl)(3-phenyl-2-phenoxy)titanium dichloride,methylene(fluorenyl)(3-tert-dichloride,methylene(fluorenyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(fluorenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,methylene(fluorenyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, isopropylidene(cyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride, isopropylidene(fluorenyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride, isopropylidene(fluorenyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,isopropylidene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, isopropylidene(fluorenyl)(3-phenyl-2-phenoxy)titaniumdichloride,isopropylidene(fluorenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(fluorenyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(fluorenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,isopropylidene(fluorenyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride, diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, diphenylmethylene(trimethylsilylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride, diphenylmethylene(fluorenyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride, diphenylmethylene(fluorenyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,diphenylmethylene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, diphenylmethylene(fluorenyl)(3-phenyl-2-phenoxy)titaniumdichloride,diphenylmethylene(fluorenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(fluorenyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(fluorenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(fluorenyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride, compounds wherein titanium of these compounds is replaced byzirconium or hafnium, compounds wherein dichloride of these compounds isreplaced by dibromide, diuodide, bis(dimethylamide), bis(diethylamide),di-n-butoxide or diisopropoxide, compounds wherein (cyclopentadienyl) ofthese compounds is replaced by (dimethylcyclopentadienyl),(trimethylcyclopentadienyl), (n-butylcyclopentadienyl),(tert-butyldimethylsilylcyclopentadienyl) or (indenyl), and compoundswherein (3,5-dimethyl-2-phenoxy) of these compounds is replaced by(2-phenoxy), (3-methyl-2-phenoxy), (3,5-di-tert-butyl-2-phenoxy),(3-phenyl-5-methyl-2-phenoxy), (3-tert-butyldimethylsilyl-2-phenoxy) or(3-trimethylsilyl-2-phenoxy); and transition metal complex wherein J isan atom of Group XIV of the Periodic Table of the Elements other thancarbon atom, such as dimethylsilyl(cyclopentadienyl)(2-phenoxy)titaniumdichloride, dimethylsilyl(cyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilyl(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(cyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(cyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilyl(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(cyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilyl(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilyl(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilyl(cyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride, dimethylsilyl(methylcyclopentadienyl)(2-phenoxy)titaniumdichloride,dimethylsilyl(methylcyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilyl(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(methylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(methylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilyl(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(methylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilyl(methylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilyl(methylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilyl(methylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride, dimethylsilyl(n-butylcyclopentadienyl)(2-phenoxy)titaniumdichloride,dimethylsilyl(n-butylcyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(n-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilyl(n-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(n-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(n-butylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(n-butylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilyl(n-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(n-butylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilyl(n-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilyl(n-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilyl(n-butylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride, dimethylsilyl(tert-butylcyclopentadienyl)(2-phenoxy)titaniumdichloride,dimethylsilyl(tert-butylcyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilyl(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(tert-butylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(tert-butylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilyl(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(tert-butylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilyl(tert-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilyl(tert-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilyl(tert-butylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride,dimethylsilyl(tetramethylcyclopentadienyl)(2-phenoxy)titaniumdichloride,dimethylsilyl(tetramethylcyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilyl(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(tetramethylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(tetramethylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilyl(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(tetramethylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilyl(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilyl(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilyl(tetramethylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride,dimethylsilyl(trimethylsilylcyclopentadienyl)(2-phenoxy)titaniumdichloride,dimethylsilyl(trimethylsilylcyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilyl(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(trimethylsilylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(trimethylsilylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilyl(trimethylsilylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(trimethylsilylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilyl(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilyl(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilyl(trimethylsilylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride, dimethylsilyl(indenyl)(2-phenoxy)titanium dichloride,dimethylsilyl(indenyl)(3-methyl-2-phenoxy)titanium dichloride,dimethylsilyl(indenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,dimethylsilyl(indenyl)(3-tert-butyl-2-phenoxy)titanium dichloride,dimethylsilyl(indenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, dimethylsilyl(indenyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride, dimethylsilyl(indenyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilyl(indenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(indenyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilyl(indenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilyl(indenyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride, dimethylsilyl(indenyl)(3,5-diamyl-2-phenoxy)titaniumdichloride, dimethylsilyl(fluorenyl)(2-phenoxy)titanium dichloride,dimethylsilyl(fluorenyl)(3-methyl-2-phenoxy)titanium dichloride,dimethylsilyl(fluorenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,dimethylsilyl(fluorenyl)(3-tert-butyl-2-phenoxy)titanium dichloride,dimethylsilyl(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(fluorenyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(fluorenyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilyl(fluorenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(fluorenyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilyl(fluorenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilyl(fluorenyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride, dimethylsilyl(fluorenyl)(3,5-diamyl-2-phenoxy)titaniumdichloride,dimethylsilyl(tetramethylcyclopentadienyl)(1-naphthox-2-yl)titaniumdichloride, compounds wherein (cyclopentadienyl) of these compounds isreplaced by (dimethylcyclopentadienyl), (trimethylcyclopentadienyl),(ethylcyclopentadienyl), (n-propylcyclopentadienyl),(isopropylcyclopentadienyl), (sec-butylcyclopentadienyl),(isobutylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl),(phenylcyclopentadienyl), (methylindenyl) or (phenylindenyl), compoundswherein (2-phenoxy) of these compounds is replaced by(3-phenyl-2-phenoxy), (3-trimethylsilyl-2-phenoxy) or(3-tert-butyldimethylsilyl-2-phenoxy), compounds wherein dimethylsilylof these compounds is replaced by diethylsilyl, diphenylsilyl ordimethoxysilyl, compounds wherein titanium of these compounds isreplaced by zirconium or hafnium, and compound wherein dichloride ofthese compounds is replaced by dibromide, diiodide, bis(dimethylamide),bis(diethylamide), di-n-butoxide or diisopropoxide.

The transition metal complex represented by the above general formula[I] can be synthesized, for example, by the following method.

That is, a compound having a structure that a group having acyclopentadienyl skeleton and a group having an alkoxybenzene skeletonare combined via an atom of Group XIV is obtained by reacting analkoxybenzene compound whose ortho-position is halogenated with acyclopentadiene compound substituted with a halogenated atom of GroupXIV in the presence of an organoalkalinemetal or a metallic magnesium.Then, a transition metal complex represented by the above generalformula [I] can be synthesized by treating the compound with a base, andreacting with a transition metal halide, a transition metal hydrocarboncompound or transition metal hydrocarbonoxy compound.

(B) Aluminum Compound

The aluminum compound (B) used in the present invention includespublicly known organoaluminum compounds, that is, one or more aluminumcompounds selected from (B1) an organoaluminum compound represented bythe general formula E¹ _(d)AlZ_(3−d), (B2) a cyclic aluminoxane having astructure represented by the general formula {—Al(E²)—O—}_(e) and (B3) alinear aluminoxane having a structure represented by the general formulaE³{—Al(E³)—O—}_(f)AlE³ ₂ (wherein E¹, E² and E³ respectively representsa hydrocarbon group, all of E¹, E² and E³ may be the same or different;Z represents a hydrogen atom or a halogen atom, and all of Z may be thesame or different; d represents a numeral satisfying 0<d≦3, e representsan integer of not less than 2: and f represents an integer of not lessthan 1). As the hydrocarbon group in E¹, E² or E³, a hydrocarbon grouphaving 1 to 8 carbon atoms is preferred and an alkyl group is morepreferred.

Specific examples of the organoaluminum compound (B1) represented by E¹_(d)AlZ_(3−d) include trialkylaluminums such as trimethylaluminum,triethylaluminum, tripropylaluminum, triisobutylaluminum,trihexylaluminum, etc.; dialkylaluminum chlorides such asdimethylaluminum chloride, diethylaluminum chloride, dipropylaluminumchloride, diusobutylaluminum chloride, dihexylaluminum chloride, etc.;alkylaluminum dichlorides such as methylaluminum dichloride,ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminumdichloride, hexylaluminum dichloride, etc.; and dialkylaluminum hydridessuch as dimethylaluminum hydride, diethylaluminum hydride,dipropylaluminum hydride, diisobutylaluminum hydride, dihexylaluminumhydride, etc.

Among them, trialkylaluminum is preferred and triethylaluminum ortriisobutylaluminum is more preferred.

Specific examples of E² and E³ in (B2) a cyclic aluminoxane having astructure represented by the general formula {—Al(E²)—O—}_(e) and (B3) alinear aluminoxane having a structure represented by the general formulaE³—{Al(E³)—O—}_(f)AlE³ ₂ include alkyl group such as methyl group, ethylgroup, n-propyl group, isopropyl group, n-butyl group, isobutyl group,n-pentyl group, neopentyl group, etc. b is an integer of not less than2, c is an integer of not less than 1. Each of E² and E³ is preferablymethyl group or isobutyl group. e is from 2 to 40 and f is from 1 to 40.

The above aluminoxane is prepared by various methods. The method is notspecifically limited, and the aluminoxane may be prepared according to apublicly known method. For example, the aluminoxane is prepared bycontacting a solution obtained by dissolving a trialkylaluminum (e.g.trimethylaluminum) in a suitable organic solvent (e.g. benzene,aliphatic hydrocarbon) with water. Also, there can be illustrated amethod for preparing the aluminoxane by contacting a trialkylaluminum(e.g. trimethylaluminum, etc.) with a metal salt containing crystalwater (e.g. copper sulfate hydrate, etc.).

(C) Boron Compound

As the boron compound (C) in the present invention, there can be usedany one of (C1) a boron compound represented by the general formulaBQ¹Q²Q³, (C2) a boron compound represented by the general formulaG⁺(BQ¹Q²Q³Q⁴)⁻ and (C3) a boron compound represented by the generalformula (L—H)⁺(BQ¹Q²Q³Q⁴)⁻.

In the boron compound (C1) represented by the general formula BQ¹Q²Q³, Brepresents a boron atom in the trivalent valence state; Q¹ to Q³ may bethe same or different and represent a halogen atom, a hydrocarbon group,a halogenated hydrocarbon group, a substituted silyl group, an alkoxygroup or a di-substituted amino group. Each of Q¹ to Q³ is preferably ahalogen atom, a hydrocarbon group having 1 to 20 carbon atoms, ahalogenated hydrocarbon group having 1 to 20 carbon atoms, a substitutedsilyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20carbon atoms or an amino group having 2 to 20 carbon atoms, morepreferably a hydrocarbon group having 1 to 20 carbon atoms or ahalogenated hydrocarbon group having 1 to 20 carbon atoms.

Specific examples of the compound (C1) includetris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane,tris(2,3,4,5-tetrafluorophenyl)borane,tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane,phenylbis(pentafluorophenyl)borane, etc., most preferablytris(pentafluorophenyl)borane.

In the boron compound (C2) represented by the general formulaG⁺(BQ¹Q²Q³Q⁴)⁻, G⁺ represents an inorganic or organic cation; Brepresents a boron atom in the trivalent valence state; and Q¹ to Q⁴ areas defined in Q¹ to Q³.

Specific examples of G⁺ as an inorganic cation in the compoundrepresented by the general formula G⁺(BQ¹Q²Q³Q⁴)⁻ include ferroceniumcation, alkyl-substituted ferrocenium cation, silver cation, etc.Examples of the G⁺ as an organic cation include triphenylmethyl cation.G⁺ is preferably a carbenium cation, particularly a triphenylmethylcation. Examples of (BQ¹Q²Q³Q⁴)⁻ includetetrakis(pentafluorophenyl)borate,tetrakis(2,3,5,6-tetrafluorophenyl)borate,tetrakis(2,3,4,5-tetrafluorophenyl)borate,tetrakis(3,4,5-trifluorophenyl)borate,tetrakis(2,2,4-trifluorophenyl)borate,phenyltris(pentafluorophenyl)borate,tetrakis(3,5-bistrifluoromethylphenyl)borate, etc.

Specific combination of them includeferroceniumtetrakis(pentafluorophenyl)borate,1,1′-dimethylferroceniumtetrakis(pentafluorophenyl)borate,silvertetrakis(pentafluorophenyl)borate,triphenylmethyltetrakis(pentafluorophenyl)borate,triphenylmethyltetrakis(3,5-bistrifluoromethylphenyl)borate, etc., mostpreferably triphenylmethyltetrakis(pentafluorophenyl)borate.

In the boron compound (C3) represented by the formula(L—H)⁺(BQ¹Q²Q³Q⁴)⁻, L represents a neutral Lewis base; (L—H)⁺ representsa Brφnsted acid; B represents a boron atom in the trivalent valencestate; and Q¹ to Q⁴ are as defined in Q¹ to Q³.

Specific examples of (L—H)⁺ as a Brφnsted acid in the compoundrepresented by the formula (L—H)⁺(BQ¹Q²Q³Q⁴)⁻ includetrialkyl-substituted ammoniums, N,N-dialkylaniliniums, dialkylammoniums,triarylphosphoniums, etc., and examples of (BQ¹Q²Q³Q⁴)⁻ include those asdefined above.

Specific combination of them includetriethylammoniumtetrakis(pentafluorophenyl)borate,tripropylammoniumtetrakis(pentafluorophenyl)borate,tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate,tri(n-butyl)ammoniumtetrakis(3,5-bistrifluoromethylphenyl)borate,N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-2,4,6-pentamethylaniliniumtetrakis (pentafluorophenyl)borate,N,N-dimethylaniliniumtetrakis(3,5-bistrifluoromethylphenyl)borate,diisopropylammoniumtetrakis (pentafluorophenyl)borate,dicyclohexylammoniumtetrakis (pentafluorophenyl)borate,triphenylphosphoniumtetrakis (pentafluorophenyl)borate,tri(methylphenyl)phosphoniumtetrakis (pentafluorophenyl)borate,tri(dimethylphenyl)phosphoniumtetrakis (pentafluorophenyl)borate, etc.,most preferably tri(n-butyl) ammoniumtetrakis(pentafluorophenyl) borateor N,N-dimethylanilinumtetrakis (pentafluorophenyl)borate.

In the production of (C1) and (C2) of the present invention, an olefinpolymerization catalyst prepared by using a transition metal complex (A)represented by the general formula [I], and [the above (B) and/or (C)]is most suitably used. In case of using an olefin polymerizationcatalyst prepared from two components (A) and (B), the above cyclicaluminoxane (B2) and/or linear aluminoxane (B3) are preferable as (B).Another preferable embodiment of the olefin polymerization catalystincludes an olefin polymerization catalyst prepared by using the above(A), (B) and (C), and in this case, the above (B1) is easily used as(B).

The respective components are desirably used so that a molar ratio of(B)/(A) is usually within the range from 0.1 to 10000, preferably 5 to2000 and a molar ratio of (C)/(A) is usually within the range from 0.01to 100, preferably 0.5 to 10.

When the respective components are used in the state of a solution orstate suspended in a solvent, the concentration of the respectivecomponents is appropriately selected according to the conditions such asability of an apparatus for feeding the respective components in apolymerization reactor. The respective components are desirably used sothat the concentration of (A) is usually from 0.01 to 500 μmol/g,preferably from 0.05 to 100 μmol/g, more preferably from 0.05 to 50μmol/g; the concentration of (B) is usually from 0.01 to 10000 μmol/g,preferably from 0.1 to 5000 μmol/g, more preferably from 0.1 to 2000μmol/g, in terms of Al atom; and the concentration of (C) is usuallyfrom 0.01 to 500 μmol/g, preferably from 0.05 to 200 μmol/g, morepreferably from 0.05 to 100 μmol/g.

As a polymerization reaction, there can be a solvent polymerization orslurry polymerization in which an aliphatic hydrocarbon such as butane,pentane, hexane, heptane, octane or the like; an aromatic hydrocarbonsuch as benzene, toluene or the like; or a halogenated hydrocarbon suchas methylene dichloride or the like used as a solvent, a gas phasepolymerization in a gaseous monomer, or the like. Further, either of acontinuous polymerization and a batch-wise polymerization are possible.

The polymerization temperature can be adopted at a range of −50° C. to250° C. and −20° C. to 100° C. in particular is preferable. Apolymerization pressure of atmospheric pressure to 60 kg/cm² G ispreferable.

In general, the polymerization time is appropriately determinedaccording to the kind of a catalyst used and a reaction apparatus, and arange of 1 minute to 20 hours can be adopted. Further, a chain transferagent such as hydrogen or the like can also be added to adjust amolecular weight of a polymer.

The above (A) and [(B) and/or (C)] may be charged to a reactor afterpreviously mixing them, or may be charged through respectively separatedinjecting pipes thereto and mixed in the reactor. And, in a system of aplurality of reaction zones, they may be charged to the first reactionzone as a whole, or may be divisionally charged to other reactionzone(s).

The olefin-based thermoplastic elastomer composition of the presentinvention contains 5 to 93% by weight of (a) and 7 to 95% by weight of(b) {(a)+(b)=100% by weight}. It contains preferably 10 to 80% by weightof (a) and 20 to 90% by weight of (b). When (a) is too little, themelt-flowability becomes insufficient, and on the other hand, when (a)is too much, the flexibility becomes insufficient.

The olefin-based thermoplastic elastomer composition of the presentinvention may contain (c) described below, in addition to theabove-mentioned (a) and (b) which are essential components.

(c): (c1) and/or (c2) described below;

(c1): a hydrogenated aromatic vinyl compound-conjugated diene compoundblock copolymer obtained by hydrogenating a block copolymer composed ofat least two polymer blocks of aromatic vinyl compounds and at least onepolymer block of conjugated diene compound, and

(c2): an ethylene-α-olefin-based copolymer rubber.

Specific examples of the aromatic vinyl compound of (c1) includestyrene, α-methylstyrene, p-methylstyrene, vinyl xylene,monochlorostyrene, dichlorostyrene, monobromostyrene, ethylstyrene,vinyl naphthalene and the like. Among these, styrene is preferable fromthe viewpoint of industrialization.

Specific examples of the conjugated diene compound of (c1) includebutadiene, isoprene, 2,3-dimethyl-1,3-butadiene,2-neopentyl-1,3-butadiene, 2-chloro-1,3-butadiene, 2-cyano-1,3-butadieneand the like. Among these, butadiene or isoprene is preferable from theviewpoint of industrialization.

(c2) includes an ethylene-α-olefin copolymer rubber and anethylene-α-olefin-non-conjugated diene copolymer rubber. Examples of theα-olefin in the ethylene-α-olefin-based copolymer rubber includepropylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-pentene, 1-octene,1-decene and the like, and among them, propylene is preferable. Further,examples of the non-conjugated diene include 1,4-hexadiene,dicyclopentadiene, 5-ethylidene-2-norbornene and the like.

An ethylene-propylene copolymer rubber is preferable from the viewpointof low temperature impact property as (c2).

The ratio of (c1)/(c2) in case of using (c1) and (c2) in combination isnot specifically limited because it differs according to a moldingmethod, and preferably 20/80 or more.

When the olefin-based thermoplastic elastomer composition contains (c),the contents of the respective components are preferably 5 to 93% byweight of (a), 5 to 93% by weight of (b) and 2 to 90% by weight of (c),and further preferably 10 to 80% by weight of (a), 10 to 80% by weightof (b) and 10 to 80% by weight of (c). {(a)+(b)+(c)=100% by weight}.When (c) is too little, low-temperature impact property is notoccasionally improved, and on the other hand, when (c) is too much, themelt-flowability becomes occasionally insufficient.

Further, according to requirement, other rubber components such as, forexample, a butadiene-based copolymer, an isoprene-based copolymer or ahydrogenated product thereof, a styrene-based thermoplastic elastomer orthe like may be added in the olefin-based thermoplastic elastomercomposition of the present invention, in addition to the above-mentionedcomponents. Moreover, a crosslinking reaction can be carried out byaddition of a peroxide, if necessary. Further, antioxidants, thermalstabilizers, ultraviolet absorbers, lubricants, antistatic agents,pigments, fillers, flame retardants, mineral oil-based softeners,foaming agents, and foaming aids may be compounded, if necessary.

It is required that the olefin-based thermoplastic elastomer compositionof the present invention has a complex dynamic viscosity η*(1) at 250°C. of 1.5×10⁵ poise or less as measured at a vibration frequency of 1radian/sec. and a Newtonian viscosity index n of 0.67 or less calculatedby the equation [I] described below;

n={log η*(1)−log η*(100)}/2  Equation [I]

(in the above-mentioned equation, η*(1) represents a complex dynamicviscosity at 250° C. measured at a vibration frequency of 1 radian/sec.,and η*(100) represents a complex dynamic viscosity at 250° C. asmeasured at a vibration frequency of 100 radian/sec.)

The complex dynamic viscosity η*(1) at 250° C. as measured at avibration frequency of 1 radian/sec. is 1.5×10⁵ poise or less,preferably 5×10³ poise or less and further preferably 3×10³ poise orless. When η*(1) is too high, the melt-flowability of the thermoplasticelastomer composition becomes insufficient, and processability in powdermolding method is deteriorated. Further, the lower limit value of η*(1)is usually 1×10² poise, preferably 3×10² poise and more preferably 5×10²poise. When η*(1) is too low, the mechanical strength of the moldedarticle obtained becomes occasionally low. Herein, the complex dynamicviscosity η*(ω) at 250° C. measured at a vibration frequency of ωradian/sec. is a value calculated by using a storage modulus G′(ω) and aloss modulus G″(ω) at 250° C. measured at a vibration frequency of ωradian/sec. according to the calculation equation [II]:

η*(ω)=(1/ω){[G′(ω)]² +[G″(ω)]²}^(1/2)  [II]

The Newtonian viscosity index n calculated by the above-mentionedequation [I] is 0.67 or less, preferably 0.01 to 0.35, and preferably0.03 to 0.25 in particular. When n is too large, the melt-flowability ofthe thermoplastic elastomer composition becomes insufficient.

The method of obtaining the thermoplastic elastomer of the presentinvention includes a method of melt-kneading by a single screw extruder,a twin screw extruder or the like.

The olefin-based thermoplastic elastomer composition for powder moldingof the present invention is processed to powder having various sizes andshapes. The powder is molded to various molded articles such as a sheet,a film or the like by powder molding method.

The powder prepared from the olefin-based thermoplastic elastomercomposition has usually an average particle diameter of 1.2 mm or less,and preferably 1.0 mm or less. When the average particle diameterexceeds 1.2 mm, the mutual fusion of the powder at the powder moldingbecomes insufficient, and pinholes, underfills and the like tend tooccur on the obtained molded article.

Further, the bulk specific gravity of the powder is preferably within arange of 0.30 to 0.65, and more preferably within a range of 0.32 to0.65, from the viewpoint of the easiness of adhering the powder on amold surface at the powder molding. When the adhesion of the powder on amold surface is insufficient, pinholes, underfills and the like are easyto occur on the molded article. The bulk specific gravity is a valuemeasured in accordance with JIS K-6721.

The powder composed of the olefin-based thermoplastic elastomercomposition, having such powder properties can be easily produced, forexample, by a method of pulverizing the thermoplastic elastomercomposition at a temperature lower than its glass transition temperature(hereinafter, referred to as “pulverization method”), further a methodof sphering the powder by solvent-treatment (hereinafter, referred to as“solvent-treatment method”. For example, refer to Japanese PatentPublication (Kokai) Sho No.62-280226.), a method of thermally fusing thethermoplastic elastomer composition, extruding it from a die to form astrand, then drawing or hauling it off while stretching, and cutting itafter cooling (hereinafter, referred to as a strand-cut method. Forexample, refer to Japanese Patent Publication (Kokai) Sho No.50-149747),a method of thermally fusing the thermoplastic elastomer composition andcutting just after the discharge opening of a die while extruding itfrom the die into water (hereinafter, referred to as a die-face cutmethod), etc.

In case of production by the pulverization method, the powder is usuallyproduced by pulverizing the thermoplastic elastomer composition at atemperature lower than its glass transition temperature. For example, afreeze pulverization method by liquid nitrogen is suitably used. Thepowder can be produced by a method of mechanically pulverizing thethermoplastic elastomer composition cooled to −70° C. or less andpreferably −90° C. or less using an impact-type pulverizer such as aball mill or the like. When the pulverization is carried out at atemperature higher than −70° C., the particle diameter of the powderprepared from the thermoplastic elastomer composition pulverized becomesrough, and it is not preferable because the powder moldability isdeteriorated. A method having little heat generation and highpulverization efficiency is preferable in order to prevent that thetemperature of the thermoplastic elastomer composition becomes higherthan the glass transition temperature at the pulverization operation. Itis preferable that a pulverization equipment itself is cooled byexternal cooling.

In case of production by the solvent-treatment method, the thermoplasticelastomer composition is pulverized at a temperature lower than theglass transition temperature, usually −70° C. or less and preferably−90° C. or less, and then solvent-treated. Herein, the solvent-treatmentmethod is a method of heating the thermoplastic elastomer compositionpulverized at a temperature higher than the melting temperature of thethermoplastic elastomer composition and preferably at a temperaturehigher by 30 to 50° C. than the melting temperature while stirring in amedium having low compatibility with the composition in the presence ofa dispersing agent and an emulsifier, sphering and then cooling it totake out.

Examples of the medium in the solvent treatment include ethylene glycol,polyethylene glycol, polypropylene glycol and the like, and the amountused is usually within the range of 300 to 1000 parts by weight per 100parts by weight of the thermoplastic elastomer composition used andpreferably 400 to 800 parts by weight.

Examples of the dispersing agent include an ethylene-acrylic acidcopolymer, silicic acid anhydride, titanium oxide and the like, and theamount used is usually within the range of 5 to 20 parts by weight per100 parts by weight of the thermoplastic elastomer composition used andpreferably 10 to 15 parts by weight.

The emulsifier include, for example, polyoxyethylene sorbitanmonolaurate, polyethylene glycol monolaurate, sorbitan tristearate andthe like, but is not limited thereto. The amount used is usually withinthe range of 3 to 15 parts by weight per 100 parts by weight of thethermoplastic elastomer composition used, and preferably 5 to 10 partsby weight.

In case of production by the strand-cut method, a diameter of adischarge opening of the die is usually within the range of 0.1 to 3 mmand preferably 0.2 to 2 mm. A discharge rate from the die is usuallywithin the range of 0.1 to 5 kg/hr/hole and preferably 0.5 to 3kg/hr/hole. A haul-off rate of a strand is usually within the range of 1to 100 m/min. and preferably 5 to 50 m/min. Further, a cut length aftercooling is usually 1.4 mm or less and preferably 1.2 mm or less.

In case of production by the die-face cut method, a diameter of adischarge opening is usually within the range of 0.1 to 3 mm andpreferably 0.2 to 2 mm. A discharge rate from the die is usually withinthe range of 0.1 to 5 kg/hr/hole and preferably 0.5 to 3 kg/hr/hole.

Further, the powder produced by the freeze-pulverization method, thesolvent-treatment method, the strand-cut method and the die-face cutmethod is occasionally referred to as pellets.

A molded article obtained by powder molding the powder prepared from thethermoplastic elastomer composition of the present invention is hardlywhitened. When the powder molding method is applied, it is suitablebecause even a complicated shape can be easily molded. Examples of thepowder molding method include a fluidization dip method, anelectrostatic coating method, a powder spray method, a powder rotationalmolding method, a powder slush molding method and the like.

In order to powder mold the powder prepared from the thermoplasticelastomer composition, for example, a mold optionally having acomplicated pattern on its molding surface is heated to a temperaturehigher than that of the powder prepared from the thermoplastic elastomercomposition, then the powder prepared from the thermoplastic elastomercomposition is fed on the molding surface of said mold, a sheet moltenarticle is obtained on said molding surface by thermally fusing thepowders each other, and then the extra powder not thermally fused isremoved. After removal of the powder, the mold may be further heated.Successively, a desired molded article can be obtained by cooling andremoving the mold.

Examples of the method of heating a mold include a gas heating furnacemethod, a heat transfer medium-circulation method, a method of dippinginto a heat transfer medium oil or a heated fluidized sand, a microwaveinduction heating method and the like. The mold temperature at thermallyfusing the powder on the mold is usually within the range of 150 to 300°C. and preferably 190 to 270° C. The time from the feed of the powder onthe molding surface of a mold till removal is not specifically limited,and is suitably selected in accordance with the size, thickness and thelike of the molded article aimed.

Further, a foamed molded article having an excellent flexibility can beproduced by molding those containing a foaming agent in the powderprepared from the thermoplastic elastomer composition.

In order to produce a foamed article by the powder molding method, thepowder prepared from the thermoplastic elastomer composition of thepresent invention, in which a foaming agent is compounded, is powdermolded and then foamed.

As the foaming agent, a thermal decomposition type foaming agent isusually used. Examples of the thermal decomposition type foaming agentinclude azo compounds such as azodicarbonamide,2,2′-azobisisobutyronitrile, diazodiaminobenzene and the like; sulfonylhydrazide compounds such as benzenesulfonyl hydrazide,benzene-1,3-sulfonyl hydrazide, p-toluenesulfonyl hydrazide and thelike; nitroso compounds such as N,N′-dinitrosopentamethylenetetramine,N,N′-dinitroso-N,N′-dimethylterephthalamide and the like; azidecompounds such as teraphthalazide and the like; and carbonates such assodium hydrogencarbonate, ammonium hydrogencarbonate, ammoniumcarbonate, and the like. Among them, azodicarbonamide is preferablyused.

As the method of producing those containing a foaming agent in thepowder prepared from the thermoplastic elastomer composition, those canbe prepared by a method of mixing a foaming agent in the powder preparedfrom the thermoplastic elastomer composition, a method of previouslykneading a foaming agent with the thermoplastic elastomer compositionbelow its decomposition temperature and then pulverizing. Further, afoaming aid and a cell adjuster may be mixed together with the foamingagent.

The molded article obtained by molding the powder prepared from thethermoplastic elastomer composition of the present invention is usefulas a skin material, and a two-layer molded article obtained bylaminating a foamed layer on one surface of the molded article may bealso used as the skin material. Such two-layer molded article can beintegrally produced by the powder molding method (refer to JapanesePatent Publication (Kokai) Hei No.5-473 and the like) and can be alsoproduced by bonding a separately produced foam to the molded articleobtained as described above with a bonding agent and the like.

To produce the two-layer molded article by the powder molding method,for example, a mold whose molding surface may be provided with acomplicated pattern is heated to a temperature higher than the meltingtemperature of the thermoplastic elastomer composition, and then thepowder prepared from the above-mentioned thermoplastic elastomercomposition is fed on the molding surface of said mold, and the powderis melted and adhered each other to obtain a sheet-like melt on themolding surface. Successively, the extra powder not thermally fused isremoved, then powder prepared from the thermoplastic polymer compositioncontaining the foaming agent is fed on this sheet-like melt and thepowder is thermally fused and adhered each other to obtain a sheet-likemelt on the molding surface. Then, the extra powder not thermally fusedis removed, and successively further heated and foamed to form a foamedlayer.

Further, it is also possible to form a composite molded article composedof a non-foam layer-a foamed layer-a non-foam layer by the powdermolding method. In this case, the non-foam layers may be the same ordifferent.

The foaming agent includes the same thermal decomposition type foamingagents as those described above. As examples of the thermoplasticpolymer composition containing the foaming agent, a expandablepolyethylene-based composition used in Japanese Patent Publication(Kokai) Hei No.7-228720 can be used in addition to those containing thefoaming agent in a vinyl chloride-based resin, a polyolefin, anolefin-based thermoplastic elastomer.

As the foamed layer, a polyurethane foamed article can be also used. Inthis case, since adhesion between the thermoplastic elastomercomposition and the polyurethane tends to be inferior, the adhesion canbe usually improved by pre-treating the adhered surface of the moldedarticle, with a primer such as a chlorinated polyethylene or the like.

Further, the polyurethane foamed article can be molded by fixing theabove-mentioned molded article and a core material described later atthe predetermined position with providing a fixed distance, injecting amixed liquid of a polyol and a polyisocyanate, and foaming underpressure.

The molded article or two-layer molded article is suitable as a skinmaterial to be laminated on a thermoplastic resin core material. Forexample, the above-mentioned molded article can be used for amulti-layer molded article obtained by laminating a thermoplastic resincore material on one surface side thereof. Further, the two-layer moldedarticle can be used for a multi-layer molded article obtained bylaminating the thermoplastic resin core material on the foamed layerside thereof.

As the thermoplastic resin in the thermoplastic resin core material, forexample, thermoplastic resins such as a polyolefin such as apolypropylene, a polyethylene or the like; an ABSresin(acrylonitrile-butadiene-styrene copolymer) and the like can beused. Among them, a polyolefin such as a polypropylene or the like ispreferably used.

The multi-layer molded article can be easily produced, for example, by amethod of feeding a thermoplastic resin melt on one surface of themolded article and pressing, or a method of feeding a thermoplasticresin melt on the foamed layer side of the two-layer molded article andpressing.

The thermoplastic resin melt means a thermoplastic resin in the moltenstate by being heated to a temperature higher than its melt temperature.The thermoplastic resin melt may be fed before or simultaneously onpressing. Further, the pressing may be carried out by using a mold orthe like, or carried out by a feeding pressure of the thermoplasticresin melt. Examples of the molding method include an injection moldingmethod, a low-pressure injection molding method, a low-pressurecompression molding method and the like.

Specifically, for example, in case of using the above-mentioned moldedarticle as the skin material, the molded article is fed between a pairof opened molds, and then both molds may be clamped after or whilefeeding a thermoplastic resin melt between one surface of the moldedarticle and one mold which is opposite to the surface. In case of usinga two-layer molded article as the skin material, the two-layer moldedarticle is fed between a pair of opened molds, and then both molds maybe clamped after or while feeding a thermoplastic resin melt between thefoamed layer of the molded article and one mold which is opposite to thefoamed layer. Herein, the opening/closing direction of both molds is notspecifically limited, and may be a vertical direction or a horizontaldirection.

When the molded article or the two-layer molded article produced byusing the fore-mentioned mold for powder molding is used as the skinmaterial, the mold for powder molding can be used as one mold in theproduction of the above-mentioned multi-layer molded article whileholding the molded article or the two-layer molded article on the moldedsurface. According to this method, since the molded article or thetwo-layer molded article to which a pattern of the mold is transferredis fed between the molds without being separated from the molds, adesired multi-layer molded article can be obtained without damaging thepattern provided on the surface.

The thermoplastic resin melt may be fed after completion of clampingboth the molds, but both the molds are preferably clamped while or afterfeeding when both the molds are not closed, because there can beobtained a multi-layer molded article wherein the molded article or thedouble-layer molded article scarcely shifts and a transfer degree of thepattern is improved. The method of feeding the thermoplastic resin meltis not specifically limited, and for example, the thermoplastic resinmelt can be fed through a resin passage provided in one mold which isopposite to the molded article or the two-layer molded article. Further,a feeding nose of the molten resin is inserted between both the molds,the molten resin is fed, and then the feeding nose may be removed out ofthe system to close both the molds.

As a pair of molds, there can be used a pair of male/female moldswherein the outer peripheral surface of the one mold and innerperipheral surface of the other mold are capable of sliding. In thiscase, by setting a clearance in sliding surface between molds to almostthe same value as that of a thickness of the molded article or thetwo-layer molded article, a multi-layer molded article having a marginalportion of the skin material around the article edges can be obtained.When the marginal portion of the skin material is folded back onto theback side of the multi-layer molded article, the multi-layer moldedarticle whose edges portion are covered with the skin material can beobtained.

The present invention is illustrated according to Examples below, butthe present invention is not limited these Examples.

Further, the evaluations of whitening on bending of the molded articleprepared from the olefin-based thermoplastic elastomer composition werecarried out according to methods below: Namely, the molded article wascut into a piece of 1 cm×5 cm and it was bent by applying a bending loadof 500 g or 1 kg. Then, the load was removed after one minute, and theevaluation was carried out on the basis of the width of the portionwhitened on bending according to the criteria described below:

1: The width of the whitened portion is 2 mm or more.

2: The width of the whitened portion is 1 mm or more and less than 2 mm.

3: The width of the whitened portion is less than 1 mm.

4: No whitened portion is recognized.

[I] Raw Material

Raw materials shown as follows were used for obtaining the respectivecompositions of Examples and Comparative Examples.

(a) Polyolefin-based Resin

An ethylene-propylene random copolymer having MI of 228 (g/10 min.) at230° C. under a load of 2.16 kg and containing 5% by weight of ethylene.

(b1) Propylene-1-butene Copolymer Rubber

The polymer produced in Reference Example (b1) described later was used.A propylene-1-butene copolymer having a Shore A hardness of 44 measuredin accordance with ASTM D2240 and an intrinsic viscosity [η] of 1.01dl/g as measured at a temperature of 70° C. in xylene (91% by mole ofpropylene, 9% by mole of butene)

(b2) Propylene-α-olefin-ethylene Copolymer Rubber

The polymer produced in Reference Example (b2) described later was used.A propylene-butene-ethylene copolymer having a Shore A hardness of 29 asmeasured in accordance with ASTM D2240 and an intrinsic viscosity [η] of0.92 dl/g measured at a temperature of 70° C. in xylene (35% by mole ofpropylene, 42% by mole of butene, 23% by mole of ethylene)

(c) Ethylene-α-olefin Copolymer Rubber

An ethylene-propylene rubber having a Mooney viscosity (ML₁₊₄ 121° C.)of 33 and a propylene content of 27% by mole.

EXAMPLE 1

Using a twin screw extruder, 40 parts by weight of (a), 40 parts byweight of (b1), 20 parts by weight of (c), and 0.2 part by weight of ananti-oxidant were kneaded at 180° C. to process pellets (a diameter of 3mm, a length of 5 mm). The pellets were cooled to −120° C., and furtherpulverized with a freeze-pulverizer to obtain the powder of theolefin-based thermoplastic elastomer composition [which was passedthrough Tyler standard sieve of 32 mesh (opening of 500 μm×500 μm)].

A nickel-electroplated mold having grains on the molding surface (15cm×15 cm×3 mm in thickness) was heated to 250° C., and 500 g of thepowder obtained as described above was sprinkled on the molding surface.After 14 seconds, the powder not fused was removed, and thefore-mentioned mold on which the fused thermoplastic elastomercomposition was mounted was laid alone for 1 minute in a furnace heatedat 250° C. After 1 minute, the mold was taken out from the furnace andcooled, and a molded article formed was removed from the mold.

The molded article had a uniform thickness (1 mm) and no pinhole. Thetest result of wrinkle-whitening on bending is shown in Table 1.

EXAMPLE 2

The same operation as in Example 1 was carried out to obtain the powderof composition, except that 40 parts by weight of (A), 40 parts byweight of (b2), 20 parts by weight of (c) and 0.2 part by weight of ananti-oxidant were used.

A nickel-electroplated mold having grains on the molding surface (15cm×15 cm, a thickness of 3 mm) was heated to 250° C., and 500 g of thepowder obtained as described above was sprinkled on the molding surface.After 14 seconds, the powder not fused was removed, and thefore-mentioned mold on which the fused thermoplastic elastomercomposition was mounted was laid alone for 1 minute in a furnace heatedat 250° C. After 1 minute, the mold was taken out from the furnace andcooled, and a molded article formed was removed from the mold.

The molded article had a uniform thickness (1 mm) and no pinhole. Thetest result of wrinkle-whitening on bending is shown in Table 1.

COMPARATIVE EXAMPLE 1

The same operation as in Example 1 was carried out to obtain the powderof composition, except that 40 parts by weight of (A), 60 parts byweight of (c) and 0.2 part by weight of an anti-oxidant were used.

A nickel-electroplated mold having grains on the molding surface (15cm×15 cm, a thickness of 3 mm) was heated to 250° C., and 500 g of thepowder obtained as described above was sprinkled on the molding surface.After 14 seconds, the powder not fused was removed, and thefore-mentioned mold on which the fused thermoplastic elastomercomposition was mounted was laid alone for 1 minute in a furnace heatedat 250° C. After 1 minute, the mold was taken out from the furnace andcooled, and a molded article formed was removed from the mold.

The molded article had a uniform thickness (1 mm) and no pinhole. Thetest result of wrinkle-whitening on bending is shown in Table 1.

TABLE 1 Test of wrinkle-whitening on bending Comparative Load Example 1Example 2 Example 1 500 g 4 4 1 1000 g 4 3 1

REFERENCE EXAMPLE Transition Metal Complex: Synthesis ofDimethylsilyl(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumDichloride

(1) Synthesis of 1-Bromo-3-tert-butyl-5-methyl-2-phenol

Under nitrogen atmosphere, 20.1 g (123 mmol) of2-tert-butyl-4-methylphenol was dissolved in 150 ml of toluene in a 500ml four necked flask equipped with a stirrer, and successively, 25.9 ml(18.0 g, 246 mmol) of tert-butylamine was added thereto. The solutionwas cooled to −70° C., and 10.5 ml (32.6 g, 204 mmol) of bromine wasadded thereto. The solution was kept at −70° C. and stirred for twohours. Then, the temperature of the solution was elevated to roomtemperature, 100 ml of 10% diluted hydrochloric acid per once was addedthereto and the solution was rinsed three times. The organic layerobtained after the rinse was dried using anhydrous sodium sulfate, thesolvent was removed using an evaporator, and then the residue waspurified using a silica gel column to obtain 18.4 g (75.7 mmol) ofcolorless oily 1-bromo-3-tert-butyl-5-methyl-2-phenol. Yield was 62%.

(2) Synthesis of 1-Bromo-3-tert-butyl-2-methoxy-5-methylbenzene

Under nitrogen atmosphere, 13.9 g (57.2 mmol) of1-bromo-3-tert-butyl-5-methyl-2-phenol synthesized in theabove-mentioned (1) was dissolved in 40 ml of acetonitrile in a 100 mlfour necked flask equipped with a stirrer, and successively, 3.8 g (67.9mmol) of potassium hydroxide was added thereto. Further, 17.8 ml (40.6g, 286 mmol) of methyl iodide was added, and the mixture was continuedto be stirred for 12 hours. Then, the solvent was removed with anevaporator, 40 ml of hexane was added to the residue, and a portionsoluble in hexane was extracted. The extraction was repeated threetimes. The solvent was removed from the extract to obtain 13.8 g (53.7mmol) of light yellow oily1-bromo-3-tert-butyl-2-methoxy-5-methylbenzene. Yield was 94%.

(3) Synthesis of(3-tert-Butyl-2-methoxy-5-methylphenyl)chlorodimethylsilane

To a solution composed of tetrahydrofuran (31.5 ml), hexane (139 ml) and1-bromo-3-tert-butyl-2-methoxy-5-methylbenzene (45 g) synthesized in theabove-mentioned (2), a 1.6 mol/l hexane solution (115 ml) of n-butyllithium was added dropwise over 20 minutes. After the obtained mixturewas kept at −40° C. for one hour, tetrahydrofuran (31.5 ml) was addeddropwise.

The mixture obtained above was added dropwise at −40° C. in a solutioncomposed of dichlorodimethylsilane (131 g) and hexane (306 ml). Thetemperature of the obtained mixture was elevated to room temperatureover 2 hours, and further stirred at room temperature for 12 hours.

The solvent and excessive dichlorodimethylsilane were distilled off fromthe reaction mixture under reduced pressure, and a portion soluble inhexane was extracted from the residue using hexane. The solvent wasdistilled off from the hexane solution obtained to obtain 41.9 g oflight yellow oily(3-tert-butyl-2-methoxy-5-methylphenyl)chlorodimethylsilane. Yield was84%.

(4) Synthesis of(3-tert-Butyl-2-methoxy-5-methylphenyl)dimethyl(tetramethylcyclopentadienyl)silane

To a solution composed of(3-tert-butyl-2-methoxy-5-methylphenyl)chlorodimethylsilane (5.24 g)synthesized in the above-mentioned (3) and tetrahydrofuran (50 ml),tetramethylcyclopentadienyllithium (2.73 g) was added at −35° C., andthe temperature of the mixture was elevated to room temperature over 2hours and further stirred at room temperature for 10 hours.

The solvent was distilled off from the reaction mixture under reducedpressure, and a portion soluble in hexane was extracted from the residueusing hexane. The solvent was distilled off from the hexane solutionobtained under reduced pressure to obtain 6.69 g of light yellow oily(3-tert-butyl-2-methoxy-5-methylphenyl)dimethyl(tetramethylcyclopentadienyl)silane. Yield was 97%.

(5) Synthesis ofDimethylsilyl(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumDichloride

To a solution composed of(3-tert-butyl-2-methoxy-5-methylphenyl)dimethyl(tetramethylcyclopentadienyl)silane(10.04 g) synthesized in the above-mentioned (4), toluene (100 ml) andtriethylamine (6.30 g), a 1.63 mol/l hexane solution (19.0 ml) ofn-butyl lithium was added dropwise, and then, the temperature of themixture was elevated to room temperature over 2 hours and further keptat room temperature for 12 hours.

Under nitrogen atmosphere, the mixture obtained above was added dropwiseat 0° C. to a toluene solution (50 ml) of titanium tetrachloride (4.82g), and then, after the temperature of the mixture was elevated to roomtemperature over 1 hour, it was refluxed by heating for 10 hours.

The reaction mixture was filtered, the solvent was distilled off fromthe filtrate, and the residue was re-crystallized from a toluene-hexanemixed solvent to obtain 3.46 g ofdimethylsilyl(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride (shown by the chemical formula as described below) of orangecolor columnar crystal. Yield was 27%.

Spectrum data were as follow.

¹H-NMR (CDCl₃): δ 0.57 (s, 6H), 1.41 (s, 9H), 2.15 (s, 6H), 2.34 (s,6H), 2.38 (s, 3H), 7.15 (s, 1H), 7.18 (s, 1H); ¹³C-NMR (CDCl₃): δ 1.25,14.48, 16.28, 22.47, 31.25, 36.29, 120.23, 130.62, 131.47, 133.86,135.50, 137.37, 140.82, 142.28, 167.74; Mass spectrum (CI, m/e): 458.

(b1) Production of Propylene-1-butene Copolymer

Propylene and 1-butene were continuously copolymerized using a 100 L SUSpolymerization vessel equipped with stirring blades. Namely, hexane iscontinuously fed as a polymerization solvent at a rate of 83 L/hr fromthe lower part of the polymerization vessel. On the other hand,polymerization solution is continuously extracted from the upper part ofthe polymerization vessel so that the polymerization solution in thepolymerization vessel is kept to 100 L in volume. As monomers, propyleneand 1-butene were continuously fed at a rate of 12.00 kg/hr and 1.33kg/hr respectively, from the lower part of the polymerization vessel inthe polymerization vessel.Dimethylsilyl(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, triphenylmethyltetrakis(pentafluorophenyl)borate andtriisobutylaluminum (hereinafter, described as TIBA in abbreviation) ascatalysts were continuously fed at a rate of 0.046 g/hr, 1.328 g/hr and2.640 g/hr, respectively, from the lower part of the polymerizationvessel in the polymerization vessel. Further, molecular weight controlwas carried out by hydrogen. The copolymerization reaction was carriedout at 50° C. by circulating cooling-water in a jacket installed on theouter part of the polymerization vessel. A small amount of ethanol wasadded in the polymerization solution extracted from the polymerizationvessel to terminate the polymerization. After removal of monomers andrinsing with water, the solvent was removed with steam in a large amountof water, and a copolymer was taken out and dried at 80° C. underreduced pressure for day and night. According to the above operation, apropylene-1-butene copolymer was obtained at a rate of 4.4 kg/hr.

(b2) Production of Propylene-1-butene-ethylene Copolymer

Ethylene, propylene and 1-butene were continuously copolymerized using a100 L SUS polymerization vessel equipped with stirring blades. Namely,hexane is continuously fed as a polymerization solvent at a rate of 83L/hr from the lower part of the polymerization vessel. On the otherhand, polymerization solution is continuously extracted from the upperpart of the polymerization vessel so that the polymerization solution inthe polymerization vessel is kept to 100 L in volume. As monomers,ethylene, propylene and 1-butene were continuously fed at a rate of 2.00kg/hr, 8.30 kg/hr and 12.70 kg/hr respectively, from the lower part ofthe polymerization vessel in the polymerization vessel.Dimethylsilyl(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, triphenylmethyltetrakis(pentafluorophenyl)borate andtruisobutylaluminum (hereinafter, described as TIBA in abbreviation) ascatalysts were continuously fed at a rate of 0.045 g/hr, 1.378 g/hr and2.640 g/hr respectively, from the lower part of the polymerizationvessel in the polymerization vessel. Further, molecular weight controlwas carried out by hydrogen. The copolymerization reaction was carriedout at 50° C. by circulating cooling-water in a jacket installed on theouter part of the polymerization vessel. A little amount of ethanol wasadded in the polymerization solution extracted from the polymerizationvessel to terminate the polymerization. After removal of monomers andrinsing with water, the solvent was removed with steam in a large amountof water, and a copolymer was taken out and dried at 80° C. underreduced pressure for day and night. According to the above operation, apropylene-1-butene copolymer was obtained at a rate of 5.0 kg/hr.

Measurement Related to Propylene-1-butene Copolymer andPropylene-1-butene-ethylene Copolymer

Measurement of the contents of propylene and 1-butene in thepropylene-1-butene copolymer and the propylene-1-butene-ethylenecopolymer was carried out according to IR method.

(1) Propylene-1-butene Copolymer

[Preparation of Calibration Curve]

Each of the mixtures of a propylene homopolymer and a 1-butenehomopolymer having various mixing ratios was molded to prepare a filmhaving a thickness of 0.05 mm by hot-pressing.

The absorption ratio of a peak (wave number: 1150 cm⁻¹) derived from thepropylene unit to a peak (wave number: 770 cm⁻¹) derived from the1-butene unit was determined using an infra-red rays photometer, and thecontents of 1-butene unit in said mixtures were plotted against theabsorption ratios. Regression straight line was determined from theseplots, and referred to as a calibration curve. Further, both of apropylene homopolymer and a 1-butene homopolymer in the mixture weredissolved in toluene, then methanol was added, and the precipitateobtained were dried to be used.

[Measurement of 1-butene Content]

The propylene-1-butene copolymer was mold to prepare a film having athickness of 0.05 mm by hot-pressing, then the absorption ratio of apeak derived from the propylene unit to a peak derived from the 1-buteneunit was determined using an infra-red photometer, and the content of1-butene unit in the propylene-1-butene copolymer was calculated fromthe calibration curve obtained by the above-mentioned method.

(2) Propylene-1-butene-ethylene Copolymer

[Preparation of Calibration Curve]

Each of the mixtures of a propylene homopolymer and a 1-butenehomopolymer having various mixing ratios was molded to make a filmhaving a thickness of 0.05 mm by heat press. The absorptions of a peak(wave number: 1150 cm⁻¹) derived from the propylene unit to a peak (wavenumber: 770 cm⁻¹) derived from the 1-butene unit were determined usingan infra-red rays photometer, and the contents of the propylene unit andthe 1-butene unit in said mixtures were plotted against the absorptions.Regression straight line was determined from these plots, and referredto as a calibration curve. Further, both of a propylene homopolymer anda 1-butene homopolymer in the mixture were dissolved in toluene, thenmethanol was added, and the precipitates obtained were dried to be used.

[Measurement of Propylene/1-butene Content]

The olefin copolymer was hot-pressed to mold a film having a thicknessof 0.05 mm, then the absorptions of a peak derived from the propyleneunit and a peak derived from the 1-butene unit were determined usinginfra-red photometer, and the contents of the propylene unit and the1-butene unit in the olefin copolymer were calculated from thecalibration curve obtained by the above-mentioned method.

The hardness of the propylene-1-butene copolymer was measured inaccordance with ASTM D2240.

The measurement of differential scanning calorimeter (DSC) was carriedout at a rate of 10° C./min. in both a temperature-elevating process anda temperature-lowering process.

The measurement of the intrinsic viscosity [η] was carried out at 70° C.in xylene using a Ubbelohde viscometer. A sample of 300 mg is dissolvedin 100 ml of xylene to prepare a solution having a concentration of 3mg/ml. The solution is further diluted to concentrations of 1/2, 1/3 and1/5, and each of the solutions is measured in a constant-temperaturewater bath of 70° C. (±0.1° C.). The measurement was repeated threetimes at the respective concentrations, and an average of the valuesobtained was used. Herein, a value obtained by setting reduced viscosity(a value determined by ((η/η₀)−1)/C when the viscosity of a solution isη, the viscosity of a solvent is η₀, and the concentration of thesolution is C) to an axis of ordinate, and setting the concentration toan axis of abscissa, is plotted. An approximate straight line is drawnfrom these points, and the extrapolated value of the reduced viscosityat a concentration of zero was referred to as the intrinsic viscosity.

Molecular weight distribution was carried out according to GelPermeation Chromatography (GPC) (manufacture by Waters Co., Ltd., and150C/GPC apparatus was used). Elution temperature was 140° C., a columnused was Shodex Packed Column A-80M manufacture by Showa-Denko K.K., andthe standard substance of molecular weight used a polystyrene(manufacture by Toso Co., Ltd., and molecular weight: 68-8,400,000). Thepolystyrene-reduced weight average molecular weight (Mw) and numberaverage molecular weight (Mn) were obtained, and further, the ratio(Mw/Mn) is referred to as the molecular weight distribution. A samplefor measurement is prepared by dissolving about 5 mg of a polymer in 5ml of o-dichlorobenzene to be a concentration of about 1 mg/ml. 400 μLof the sample solution obtained was injected, the flow rate of elutionsolvent was 1.0 ml/min., and it was detected by a refractive indexdetector.

INDUSTRIAL APPLICABILITY

As described above, according to the present invention, an olefin-basedthermoplastic elastomer composition for powder molding, which makes thebest use of the merit of an olefin-based material such as no generationof poisonous gas at incineration and is hardly whitened on bending andexcellent in flexibility; powder for powder molding prepared from thecomposition; and a molded article obtained by powder molding the powder;can be provided.

What is claimed is:
 1. An olefin-based thermoplastic elastomercomposition for powder molding, which comprises 5 to 93% by weight of(a) and 7 to 95% by weight of (b) described below, and has a complexdynamic viscosity η*(1) at 250° C. of 1.5×10⁵ poise or less as measuredat a vibration frequency of 1 radian/sec. and a Newtonian viscosityindex n of 0.67 or less as calculated by the equation [I] describedbelow: (a) a polyolefin-based resin; (b) at least one of (b1) and (b2):(b1) a propylene-1-butene-based copolymer rubber having a Shore Ahardness of 70 or less as measured in accordance with ASTM D2240 and anintrinsic viscosity [η] of 0.3 dl/g or more as measured at a temperatureof 70° C. in xylene, (b2) a propylene-α-olefin-ethylene-based copolymerrubber having a Shore A hardness of 70 or less as measured in accordancewith ASTM D2240 and an intrinsic viscosity [η] of 0.3 dl/g or more asmeasured at a temperature of 70° C. in xylene and comprising propylene,an α-olefin having 4 to 20 carbon atoms, and ethylene; and n={(logη*(1)−log η*(100)}/2; wherein η*(1)  equation [I] represents a complexdynamic viscosity at 250° C. measured at a vibration frequency of 1radian/sec., and η*(100) represents a complex dynamic viscosity at 250°C. measured at a vibration frequency of 100 radian/sec.
 2. Theolefin-based thermoplastic elastomer composition for powder moldingaccording to claim 1, wherein (a) is a propylene-based polymer.
 3. Theolefin-based thermoplastic elastomer composition for powder moldingaccording to claim 1, wherein (b1) has neither crystal-melting peak norcrystallization peak at measurement by a differential scanningcalorimeter (DSC).
 4. The olefin-based thermoplastic elastomercomposition for powder molding according to claim 1, wherein (b1) has amolecular weight distribution (Mw/Mn) of 3 or less at measurement by gelpermeation chromatography.
 5. The olefin-based thermoplastic elastomercomposition for powder molding according to claim 1, wherein (b2) hasneither crystal-melting peak nor crystallization peak at measurement bya differential scanning calorimeter.
 6. The olefin-based thermoplasticelastomer composition for powder molding according to claim 1, wherein(b2) has a molecular weight distribution (Mw/Mn) of 3 or less atmeasurement by gel permeation chromatography.
 7. Powder for powdermolding prepared from the olefin-based thermoplastic elastomercomposition of claim
 1. 8. Powder for powder molding according to claim7, produced by a pulverization method, a solvent-treatment method, astrand cut method or a die-face cut method.
 9. Powder for powder moldingaccording to claim 7, wherein a sphere-reduced average particle diameteris 1.2 mm or less.
 10. A molded article obtained by powder molding thepowder for powder molding according to claim 7.